The present invention relates to a novel carbamate derivative and an agricultural/horticultural fungicide containing said derivative as the active ingredient.
Heretofore, many carbamic acid derivatives have been reported, but it has not been known that a carbamic acid derivative having an oxime ether group in a phenyl group as the compound of the present invention has excellent fungicidal activities.
The object of the present invention is to provide a novel carbamate derivative and an agricultural/horticultural fungicide containing the same as the active ingredient.
The present inventors have conducted extensive studies to produce a novel agricultural/horticultural fungicide and as a result, have found that the carbamate derivative of the present invention (hereinafter referred to as compound of the present invention) is a novel compound not disclosed in any literatures and have outstanding effects as an agricultural/horticultural fungicide, and have finally accomplished the present invention. Namely, the present invention resides in (1) a carbamate derivative represented by the general formula [I]: 
{wherein X is a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkyl group or a C1-C6 haloalkoxy group, n is 0 or an integer of from 1 to 4, R1 is a C1-C6 alkyl group, R2 is a hydrogen atom, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkoxy group, a C1-C6 alkoxy C1-C6 alkyl group, a C1-C6 alkylcarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylcarbonyl C1-C6 alkyl group or a benzyl group which may be substituted, R3 is a hydrogen atom or a C1-C6 alkyl group, G is an oxygen atom, a sulfur atom or a xe2x80x94NR4xe2x80x94 group [wherein R4 is a hydrogen atom or a C1-C6 alkyl group], Y is a hydrogen atom, a C1-C10 alkyl group (said group may be substituted by the same or different at least one halogen atom, cyano group, nitro group, hydroxyl group, C3-C6 cycloalkyl group, C1-C6 alkoxy group, amino group, mono C1-C6 alkylamino group, di-C1-C6 alkylamino group, C1-C6 alkylthio group, C1-C6 alkylsulfinyl group, carboxyl group, C1-C6 alkylcarbonyl group, C1-C6 alkoxycarbonyl group, C1-C6 alkoxyimino group or C(O)NR5R6 (wherein each of R5 and R6 which are the same or different, is a hydrogen atom or a C1-C6 alkyl group)), a C2-C10 alkenyl group (said group may be substituted by the same or different at least one halogen atom, cyano group, nitro group, hydroxyl group, C1-C6 alkoxy group, amino group, mono C1-C6 alkylamino group, di-C1-C6 alkylamino group, C1-C6 alkylthio group, C1-C6 haloalkyl group, C1-C6 alkylcarbonyl group, C1-C6 alkoxycarbonyl group or C(O)NR5R6 (wherein each of R5 and R6 which are the same or different, is a hydrogen atom or a C1-C6 alkyl group)), a C2-C10 alkynyl group (said group may be substituted by the same or different at least one halogen atom, cyano group, nitro group, cycloalkyl group, hydroxyl group, C1-C6 alkoxy group, amino group, mono C1-C6 alkylamino group, di-C1-C6 alkylamino group, C1-C6 alkylthio group, C1-C6 haloalkyl group, C1-C6 alkylcarbonyl group, C1-C6 alkoxycarbonyl group or C(O)NR5R6 (wherein each of R5 and R6 which are the same or different, is a hydrogen atom or a C1-C6 alkyl group)), a C3-C6 cycloalkyl group (said group may be substituted by the same or different at least one halogen atom, cyano group, nitro group, C1-C6 alkyl group, C2-C6 alkenyl group, C2-C6 alkynyl group, hydroxyl group, C1-C6 alkoxy group, amino group, mono C1-C6 alkylamino group, di-C1-C6 alkylamino group, C1-C6 alkylthio group, C1-C6 haloalkyl group, C1-C6 alkylcarbonyl group, C1-C6 alkoxycarbonyl group or C(O)NR5R6 (wherein each of R5 and R6 which are the same or different, is a hydrogen atom or a C1-C6 alkyl group)), a C3-C6 cycloalkenyl group (said group may be substituted by the same or different at least one halogen atom, cyano group, nitro group, C1-C6 alkyl group, C2-C6 alkenyl group, hydroxyl group, C2-C6 alkynyl group, amino group, mono C1-C6 alkylamino group, di-C1-C6 alkylamino group, C1-C6 alkoxy group, C1-C6 alkylthio group, C1-C6 haloalkyl group, C1-C6 alkylcarbonyl group, C1-C6 alkoxycarbonyl group or C(O)NR5R6 (wherein each of R5 and R6 which are the same or different, is a hydrogen atom or a C1-C6 alkyl group)), a phenacyl group (said group may be substituted by the same or different at least one halogen atom, C1-C6 alkyl group, C1-C6 alkoxy group, C1-C6 haloalkyl group, C1-C6 alkylcarbonyl group or C1-C6 alkoxycarbonyl group), an aryl group (said group may be substituted by the same or different at least one halogen atom, cyano group, nitro group, C1-C6 alkyl group, C2-C6 alkenyl group, C2-C6 alkynyl group, hydroxyl group, C1-C6 alkoxy group, amino group, mono C1-C6 alkylamino group, di-C1-C6 alkylamino group, C1-C6 alkylthio group, C1-C6 haloalkyl group, C1-C6 alkylcarbonyl group, C1-C6 alkoxycarbonyl group or C(O)NR5R6 (wherein each of R5 and R6 which are the same or different, is a hydrogen atom or a C1-C6 alkyl group)), a heteroaryl group (said group may be substituted by the same or different at least one halogen atom, cyano group, nitro group, C1-C6 alkyl group, C2-C6 alkenyl group, C2-C6 alkynyl group, hydroxyl group, C1-C6 alkoxy group, amino group, mono C1-C6 alkylamino group, di-C1-C6 alkylamino group, C1-C6 alkylthio group, C1-C6 haloalkyl group, C1-C6 alkylcarbonyl group, C1-C6 alkoxycarbonyl group or C(O)NR5R6 (wherein each of R5 and R6 which are the same or different, is a hydrogen atom or a C1-C6 alkyl group)), an aryl-C1-C6 alkyl group (the aryl in said group may be substituted by the same or different at least one halogen atom, cyano group, nitro group, C1-C6 alkyl group, C2-C6 alkenyl group, C2-C6 alkynyl group, phenoxy group which may be substituted, hydroxyl group, C1-C6 alkoxy group, amino group, mono C1-C6 alkylamino group, di-C1-C6 alkylamino group, C1-C6 alkylthio group, C1-C6 haloalkyl group, C1-C6 haloalkoxy group, C1-C6 alkylcarbonyl group, C1-C6 alkoxycarbonyl group, C1-C6 alkoxyimino C1-C6 alkyl group or C(O)NR5R6 (wherein each of R5 and R6 which are the same or different, is a hydrogen atom or a C1-C6 alkyl group)), an aryl-C2-C6 alkenyl group (the aryl in said group may be substituted by the same or different at least one halogen atom, cyano group, nitro group, C1-C6 alkyl group, C2-C6 alkenyl group, C2-C6 alkynyl group, hydroxyl group, C1-C6 alkoxy group, amino group, mono C1-C6 alkylamino group, di-C1-C6 alkylamino group, C1-C6 alkylthio group, C1-C6 haloalkyl group, C1-C6 alkylcarbonyl group, C1-C6 alkoxycarbonyl group or C(O)NR5R6 (wherein each of R5 and R6 which are the same or different, is a hydrogen atom or a C1-C6 alkyl group)) or a heterocyclic-C1-C6 alkyl group (the heterocycle in said group may be substituted by the same or different at least one halogen atom, cyano group, nitro group, C1-C6 alkyl group, C2-C6 alkenyl group, C2-C6 alkynyl group, hydroxyl group, C1-C6 alkoxy group, amino group, mono C1-C6 alkylamino group, di-C1-C6 alkylamino group, C1-C6 alkylthio group, C1-C6 haloalkyl group, C1-C6 alkylcarbonyl group, C1-C6 alkoxycarbonyl group or C(O)NR5R6 (wherein each of R5 and R6 which are the same or different, is a hydrogen atom or a C1-C6 alkyl group)), and Q is a hydrogen atom, a haloalkyl group, a cyano group, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C1-C4 alkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 alkylsulfonyl group or a phenyl group (said group may be substituted by at least one halogen atom, cyano group, nitro group, C1-C4 alkyl group, C2-C4 alkenyl group, C2-C4 alkynyl group, hydroxyl group, C1-C4 alkoxy group, C1-C4 haloalkyl group, C1-C4 haloalkoxy group, C1-C4 alkylcarbonyl group or C1-C4 alkoxycarbonyl group)}, and (2) an agricultural/horticultural fungicide containing the same as the active ingredient.
Symbols and terms used in the present specification will be explained.
The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
A notation such as C1-C10 indicates that the carbon number of a substituent following this notation is from 1 to 10 in this case.
The C1-C6 alkyl group is a straight chain or branched chain alkyl group and may, for example, be methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, neopentyl, n-hexyl, 1,1-dimethylpropyl or 1,1-dimethylbutyl.
The C1-C10 alkyl group may, for example, be the above-mentioned C1-C6 alkyl group, or a group such as heptyl, octyl, 1,1-diethylbutyl, nonyl or decyl.
The C3-C6 cycloalkyl group may, for example, be a group such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
The C3-C6 cycloalkenyl group may, for example, be a group such as 1-cyclopenten-1-yl, 2-cyclopenten-1-yl, 1-cyclohexen-1-yl or 2-cyclohexen-1-yl.
The C1-C6 haloalkyl group is a straight chain or branched chain alkyl group substituted by a halogen atom and may, for example, be a group such as fluoromethyl, chloromethyl, difluoromethyl, dichloromethyl, trifluoromethyl or pentafluoroethyl.
The C2-C10 alkenyl group is a straight chain or branched chain alkenyl group and may, for example, be vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-hexenyl or 1-octenyl.
The C2-C10 alkynyl group is a straight chain or branched chain alkynyl group and may, for example, be a group such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 4-methyl-1-pentynyl or 3-methyl-1-pentynyl.
The C1-C6 alkoxy group is an alkyloxy group wherein the alkyl moiety has the above meaning and may, for example, be a group such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isopentyloxy or n-hexyloxy.
The C1-C6 haloalkoxy group is a haloalkyloxy group wherein the haloalkyl moiety has the above meaning and may, for example, be a group such as fluoromethoxy, difluoromethoxy, trifluoromethoxy or pentafluoroethoxy.
The C1-C6 alkoxyimino group is an alkoxyimino group wherein the alkoxy moiety has the above meaning and may, for example, be a group such as methoxyimino.
The C1-C6 alkoxyimino C1-C6 alkyl group is an alkoxyiminoalkyl group wherein the alkoxy moiety and the alkyl moiety have the above meanings and may, for example, be a group such as 1-methoxyiminoethyl.
The C1-C6 alkylcarbonyl group is an alkylcarbonyl group wherein the alkyl moiety has the above meaning, and may, for example, be a group such as acetyl, propionyl, butyryl, isobutyryl, pivaloyl or hexanoyl.
The C1-C6 alkoxycarbonyl group is an alkoxycarbonyl group wherein the alkoxy moiety has the above meaning and may, for example, be a group such as methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl or hexyloxycarbonyl.
The C1-C6 alkylcarbonyl C1-C6 alkyl group is an alkylcarbonylalkyl group wherein the alkyl moiety has the above meaning and may, for example, be a group such as a 2-oxypropyl group, a 3-oxobutyl group, a 3-oxopentyl group or a 3,3-dimethyl-2-oxobutyl group.
The aryl group is an aromatic hydrocarbon group and may, for example, be a group such as phenyl, 1-naphthyl or 2-naphthyl.
The heterocyclic-C1-C6 alkyl group is a 3- to 10-membered cycle wherein the alkyl moiety is xe2x80x94CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH(Me)xe2x80x94, xe2x80x94C(Me)2xe2x80x94, xe2x80x94CH(Et)xe2x80x94 or the like, and the heterocyclic moiety is constituted of from 2 to 9 carbon atoms, from 0 to 3 nitrogen atoms, from 0 to 3 oxygen atoms and from 0 to 3 sulfur atoms, and may, for example, be a group such as pyrrolyl, furyl, thienyl, pyrazolyl, isoxazolyl, isothiazolyl, imidazolyl, oxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzofuryl, benzothienyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, quinolyl, isoquinolyl, morpholino, oxyranyl or dioxacyclopentyl.
The heteroaryl group is a 5- to 10-membered heterocyclic aromatic ring group constituted of from 2 to 9 carbon atoms, from 0 to 3 nitrogen atoms, from 0 to 3 oxygen atoms and from 0 to 3 sulfur atoms, and may, for example, be a heterocycle such as pyrrolyl, furyl, thienyl, pyrazolyl, isoxazolyl, isothiazolyl, imidazolyl, oxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzofuryl, benzothienyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, quinolyl or isoquinolyl.
The C1-C6 alkoxy C1-C6 alkyl group is a group wherein the alkyl moiety and the alkoxy moiety have the above meanings and may, for example, be a group such as methoxymethyl, ethoxymethyl, isopropoxymethyl, pentyloxymethyl, methoxyethyl or butoxyethyl.
The mono C1-C6 alkylamino group is a group wherein the alkyl moiety has the above meaning and may be a group such as methylamino, ethylamino, isopropylamino, butylamino or tert-butylamino.
The di-C1-C6 alkylamino group is a group wherein each of the alkyl moieties which are the same or different, has the above meaning, and may, for example, be a group such as dimethylamino, diethylamino, methylethylamino, methylisopropylamino or dihexylamino.
The C1-C6 alkylthio group is a group wherein the alkyl moiety has the above meaning and may be a group such as methylthio, ethylthio, isopropylthio, butylthio or hexylthio.
The C1-C6 alkylsulfinyl group is a group wherein the alkyl moiety has the above meaning and may be a group such as methylsulfinyl, ethylsulfinyl, isopropylsulfinyl, butylsulfinyl or hexylsulfinyl.
The C1-C6 alkylsulfonyl group is a group wherein the alkyl moiety has the above meaning and may be a group such as methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, butylsulfonyl or hexylsulfonyl.
The aryl C1-C6 alkyl group is a group wherein the aryl moiety has the above meaning and the alkyl moiety is xe2x80x94CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH(Me)xe2x80x94, xe2x80x94C(Me)2xe2x80x94, xe2x80x94CH(Et)xe2x80x94 or the like.
The aryl C1-C6 alkenyl group is a group wherein the aryl moiety has the above meaning and the alkenyl moiety is xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94CHxe2x95x90CHCH2xe2x80x94, xe2x80x94C(Me)xe2x95x90CHxe2x80x94, xe2x80x94CH(Et)xe2x95x90(CH)xe2x80x94, xe2x80x94C(Me)xe2x95x90CHCH2xe2x80x94 or the like.
The heteroaryl C1-C6 alkyl group is a group wherein the heteroaryl moiety has the above meaning and the alkyl moiety is xe2x80x94CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH(Me)xe2x80x94, xe2x80x94(Me)2xe2x80x94, xe2x80x94CH(Et)xe2x80x94 or the like.
Now, specific examples of the compound of the present invention represented by the general formula [I] will be described in Tables 1 to 13. However, the compound of the present invention is not limited to such compounds. Here, the compound Nos. will be referred to in the subsequent description.
Symbols in the Tables have the following meanings respectively. Me represents a methyl group, Et represents an ethyl group, Pr represents a n-propyl group, Pr-i represents an iso-propyl group, Bu represents a n-butyl group, Bu-i represents an iso-butyl group, Bu-s represents a sec-butyl group, Bu-t represents a tert-butyl group, Hex represents a n-hexyl group, Pr-c represents a cyclopropyl group, Pen-c represents a cyclopentyl group, Hex-c represents a cyclohexyl group, and Ph represents a phenyl group. Further, Ph(4-Cl) represents a 4-chlorophenyl group for example.
Some of the compounds of the present invention represented by the general formula [I] have one or from 2 to 3 double bonds relating to E/Z isomers in their molecules, and with respect to such compounds, E/Z isomer mixtures are present. Pure individual E-forms and Z-forms and their mixtures are also included in the compounds of the present invention. The following pairs of compounds are geometrical isomers relating to oxime portion double bond (A-80 and A-206, A-84 and A-207, A-85 and A-208, A-86 and A-209, A-286 and A-448).
Typical processes for producing the carbamate derivative represented by the general formula [I] as the compound of the present invention, will be exemplified below. Here, the novel compound represented by the general formula [I] has a Cxe2x95x90N double bond and thereby may form as an E/Z isomer mixture in some cases. The isomer mixture can be isolated into individual component by a purification method such as crystallization or column chromatography. An individual isomer and a mixture thereof are included in the present invention. 
(wherein each of G, R1, R2, R3, Q, X, Y and n is as defined above.)
The compound [I] of the present invention can be produced by reacting a compound [II] and a compound [III] in an inert solvent (see Jikken kagaku Kouza (Experimental Chemical Lecture), fourth edition, vol. 20, p. 349-355 (The Chemical Society of Japan) for example). Here, the material compound [III] to be used in the present production process may form a salt with e.g. hydrochloric acid or sulfuric acid. The compound [III] may be produced in accordance with a known process (see Jikken kagaku Kouza, fourth edition, vol. 20, p. 342-349 for example).
With respect to the amount of the material compound to be used in the present reaction, the compound [III] is properly selected within a range of from 1 to 50 equivalents based on the compound [II], preferably from 1 to 10 equivalents. The inert solvent which can be used in the present production process may, for example, be an alcohol such as methanol, ethanol, propanol or isopropanol, an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane or diethylene glycol dimethyl ether, an aromatic hydrocarbon such as benzene, chlorobenzene, nitrobenzene or toluene, or water. These inert solvents may be used alone or as mixed.
In the present production process, an acid such as hydrochloric acid or acetic acid, or a base such as sodium acetate, sodium carbonate or sodium hydrogencarbonate, may coexist, and they may be used alone or in combination. The amount is properly selected within a range of from 0.001 to 50 equivalents based on the compound [II], preferably from 0.01 to 10 equivalents. The reaction temperature is within a range of from xe2x88x9210xc2x0 C. to the boiling point of the inert solvent to be used, and preferably within a range of from 0xc2x0 C. to the boiling point of the inert solvent to be used. The reaction time varies depending upon e.g. the reaction temperature and the reaction amount, but may be selected within a range of from 1 to 48 hours in general. After completion of the reaction, the desired product is isolated from the reaction system by a conventional method and may be purified by e.g. column chromatography or recrystallization, as the case requires. 
(wherein each of G, R1, R2, R3, X and n is as defined above, Qxe2x80x2 is a cyano group or a nitro group, and A is a C1-C10 alkyl group.)
A compound [I-a] of the present invention can be produced by reacting a compound [IV] and a nitrite ester [V] in the presence of a base (see Organic Syntheses, vol. 6, p.199 (1988) for example). With respect to the amount of the material compound to be used in the present reaction, the compound [V] is properly selected within a range of from 1 to 50 equivalents based on the compound [IV], preferably from 1 to 10 equivalents.
The base to be used in the present production process may, for example, be an alkali metal alcoholate such as sodium methoxide, sodium ethoxide or potassium tert-butoxide, or an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, and the amount of the base is properly selected within a range of from 0.5 to 50 equivalents based on the compound [IV], preferably from 1 to 10 equivalents.
The inert solvent which can be used in the present production process may be one which does not inhibit the progress of the present production process, and an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane or diethylene glycol dimethyl ether, a halogenated hydrocarbon such as dichloromethane, chloroform, carbon tetrachloride or tetrachloroethane, an aromatic hydrocarbon such as benzene, chlorobenzene or toluene, or an alcohol such as methanol, ethanol, propanol or isopropanol, may, for example, be used. These inert solvents may be used alone or as mixed.
The reaction temperature is within a range of from xe2x88x9270xc2x0 C. to the boiling point of the inert solvent to be used, and preferably from xe2x88x9220xc2x0 C. to the boiling point of the inert solvent to be used. The reaction time varies depending upon e.g. the reaction temperature and the reaction amount, but may be selected within a range of from 1 to 100 hours in general, preferably from 12 to 75 hours.
After completion of the reaction, the desired product is isolated from reaction system by a conventional method and may be purified by e.g. column chromatography or recrystallization, as the case requires. 
(wherein each of G, R1, R2, R3, X, Q and n is as defined above, Yxe2x80x2 has the same meaning as the above-mentioned Y except for hydrogen, and L is a leaving group and is a halogen atom or a sulfonate such as tosyloxy or mesyloxy.)
A compound [I-e] of the present invention can be produced by reacting a compound [I-b] of the present invention and a compound [VI] in the presence of a base.
With respect to the amount of the material compound to be used in the present reaction, the compound [VI] is properly selected within a range of from 1 to 50 equivalents based on the compound [I-b], preferably from 1 to 5 equivalents.
An inert solvent may be used in the present production process in some cases. The inert solvent may be one which does not inhibit the progress of the present reaction, and a ketone such as acetone, methyl ethyl ketone or cyclohexanone, an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane or diethylene glycol dimethyl ether, an ester such as ethyl acetate or methyl acetate, a halogenated hydrocarbon such as dichloromethane, chloroform or carbon tetrachloride, an aromatic hydrocarbon such as benzene, chlorobenzene, nitrobenzene or toluene, a nitrile such as acetonitrile, or N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolinone or dimethylsulfoxide may, for example, be used. These inert solvents may be used alone or as mixed.
As the base which can be used, an alkali metal hydride such as sodium hydride, an alkali metal alcoholate such as potassium tert-butoxide, or an inorganic salt such as sodium carbonate or potassium carbonate may, for example, be used. The amount of the base may properly be selected within a range of from 1 to 50 equivalents based on the compound [I-b], preferably from 1 to 10 equivalents.
The reaction temperature is within a range of from xe2x88x9270xc2x0 C. to the boiling point of the inert solvent to be used, preferably within a range of from 0xc2x0 C. to the boiling point of the inert solvent to be used. The reaction time varies depending upon e.g. the reaction temperature and the reaction amount, but may be selected within a range of from 1 hour to 72 hours in general. After completion of the reaction, the desired product is isolated from the reaction system by a conventional method and may be purified by e.g. column chromatography or recrystallization, as the case requires. 
{wherein each of G, Q, R1, R2, R3, X, Y and n is as defined above, and Lxe2x80x2 is a halogen atom.}
A compound [VIII] can be produced by halogenating a compound [VII] by a known process (see Jikken kagaku Kouza fourth edition, vol. 19, p. 416-482 (The Chemical Society of Japan) for example) (Step 4.1). A compound [I-c] of the present invention can be produced by reacting the compound [VIII] with a compound [IX] in the presence of a base in an inert solvent (Step 4.2). Further, a compound [I-d] of the present invention can be produced by reacting the compound [VIII] with an alkali metal cyanate salt and a compound [X] in an inert solvent (see Journal of the Chemical Society of Japan, vol. 87, No. 5, p. 486 (1966) for example) (Step 4.3).
The halogenating agent which can be used in Step 4.1 of the present production process may, for example, be N-bromosuccinimide, N-chlorosuccinimide or trichloroisocyanuric acid. The amount of the halogenating agent is properly selected within a range of from 0.5 to 10 equivalents based on the compound [VII], preferably from 1 to 3 equivalents. A catalyst such as azobisisobutyronitrile or benzoyl peroxide may be used in the present step, and its amount is properly selected within a range of from 0.001 to 10 equivalents based on the compound [VII], preferably from 0.001 to 1 equivalents.
The inert solvent may be one which does not inhibit the progress of Step 4.1, and a halogenated hydrocarbon such as dichloromethane, chloroform or carbon tetrachloride or an aromatic hydrocarbon such as benzene or chlorobenzene may, for example, be used.
The reaction temperature is within a range of from 0xc2x0 C. to the boiling point of the inert solvent to be used. The reaction time varies depending upon e.g. the reaction temperature and the reaction amount, but may be selected within a range of from several minutes to 48 hours in general. After completion of the reaction, the desired product is isolated from the reaction system by a conventional method and may be purified by e.g. column chromatography or recrystallization, as the case requires.
With respect to the amount of the material compound [IX] to be used in Step 4.2 of the present production process, it is properly selected within a range of from 1 to 50 equivalents based on the compound [VIII], preferably from 1 to 10 equivalents.
As the base to be used, an inorganic salt such as sodium carbonate, potassium carbonate or sodium hydrogencarbonate or an alkali metal hydride such as sodium hydride may be used, and the amount of the base is properly selected within a range of from 0.5 to 100 equivalents based on the compound [VIII], preferably from 1 to 10 equivalents.
The inert solvent which can be used may be one which does not inhibit the progress of Step 4.2, and a ketone such as acetone, methyl ethyl ketone or cyclohexanone, an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, monoglyme or diglyme, an ester such as ethyl acetate or methyl acetate, a halogenated hydrocarbon such as dichloromethane, chloroform or carbon tetrachloride, an aromatic hydrocarbon such as benzene, chlorobenzene, nitrobenzene or toluene, a nitrile such as acetonitrile, an alcohol such as methanol, ethanol or butanol, or N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl 2-imidazolinone or dimethylsulfoxide may, for example, be used, and these inert solvents may be used alone or as mixed.
The reaction temperature is within a range of from xe2x88x9270xc2x0 C. to the boiling point of the inert solvent to be used, and preferably from xe2x88x9210xc2x0 C. to the boiling point of the inert solvent to be used. The reaction time varies depending upon e.g. the reaction temperature and the reaction amount, but may be selected within a range of from several minutes to 48 hours in general. After completion of the reaction, the desired product is isolated from the reaction system by a conventional method and may be purified by e.g. column chromatography or recrystallization, as the case requires.
The alkali metal cyanate salt which can be used in Step 4.3 of the present production process may, for example, be potassium cyanate or sodium cyanate. The amount of the metal cyanate salt to be used is properly selected within a range of from 1 to 50 equivalents based on the compound [VIII], preferably from 1 to 10 equivalents, and the compound [X] is properly selected within a range of from 1 to 100 equivalents based on the compound [VIII], preferably from 1 to 20 equivalents. The inert solvent which can be used may be one which does not inhibit the progress of Step 4.3, and a ketone such as acetone, methyl ethyl ketone or cyclohexanone, an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, monoglyme or diglyme, an ester such as ethyl acetate or methyl acetate, a halogenated hydrocarbon such as dichloromethane, chloroform or carbon tetrachloride, an aromatic hydrocarbon such as benzene, chlorobenzene, nitrobenzene or toluene, a nitrile such as acetonitrile, an alcohol such as methanol, ethanol or butanol, or N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolinone or dimethylsulfoxide may, for example, be used, and these inert solvents may be used alone or as mixed.
The reaction temperature is within a range of from 0xc2x0 C. to the boiling point of the inert solvent to be used. The reaction time varies depending upon e.g. the reaction temperature and the reaction amount, but may be selected within a range of form 1 hour to 48 hours in general. After completion of the reaction, the desired product is isolated from the reaction system by a conventional method and may be purified by e.g. column chromatography or recrystallization, as the case requires. 
{wherein each of G, R1 and R3 is as defined above, each of X1, X2, X3 and X4 is a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkyl group or a C1-C6 haloalkoxy group, Qxe2x80x3 is a hydrogen atom, a haloalkyl group, a C1-C6 alkyl group, a C3-C6 cycloalkyl group or a phenyl group (said group may be substituted by at least one halogen atom, cyano group, nitro group, C1-C4 alkyl group, C2-C4 alkenyl group, C2-C4 alkynyl group, hydroxyl group, C1-C4 alkoxy group, C1-C4 haloalkyl group, C1-C4 haloalkoxy group, C1-C4 alkylcarbonyl group or C1-C4 alkoxycarbonyl group).}
A compound [I-f] of the present invention can be produced by diazotizing a compound [XVIII] by sodium nitrite in the presence of e.g. hydrochloric acid in accordance with a known process, and reacting a compound [XIX] therewith in the presence of e.g. sodium acetate and copper sulfate (see Organic Syntheses vol. 5, p. 139 (1973) for example).
With respect to the amount of the material compound to be used in the present reaction, the compound [XIX] is properly selected within a range of from 1 to 50 equivalents based on the compound [XVIII], preferably from 1 to 5 equivalents.
The solvent which can be used in the present production process may be one which does not inhibit the progress of the present reaction. For example, an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane or diethylene glycol dimethyl ether, an ester such as ethyl acetate or methyl acetate, a halogenated hydrocarbon such as dichloromethane, chloroform or carbon tetrachloride, an aromatic hydrocarbon such as benzene, chlorobenzene, nitrobenzene or toluene, an organic acid such as acetic acid or trifluoroacetic acid, or water may, for example, be used, and these solvents may be used alone or as mixed.
As the acid to be used in Step 1) diazotization of the present production process, a strong acid such as sulfuric acid, tetrafluoroboric acid, hydrobromic acid or trifluoroacetic acid may be used instead of the above-mentioned hydrochloric acid. The amount is properly selected within a range of from 1 to 50 equivalents based on the compound [XVIII], preferably from 2 to 4 equivalents. Further, a nitrite ester such as isoamyl nitrite or methyl nitrite may be used instead of the above-mentioned sodium nitrite. The amount is properly selected within a range of from 1 to 50 equivalents based on the compound [XVIII], preferably from 1 to 2 equivalents. The reaction temperature is within a range of from xe2x88x9220xc2x0 C. to 30xc2x0 C., preferably within a range of from xe2x88x925xc2x0 C. to 5xc2x0 C. The reaction time varies depending upon e.g. the reaction temperature and the reaction amount, but may be selected within a range of from 30 minutes to 2 hours in general. As the copper compound to be used in Step 2) of coupling in the present reaction, a copper salt such as copper(I) chloride or copper(II) acetate may be used instead of the above-mentioned copper sulfate. The amount is properly selected within a range of from 0.02 to 2 equivalents based on the compound [XVIII], preferably from 0.02 to 0.5 equivalent. Further, the amount of sodium acetate is properly selected within a range of from 1 to 50 equivalents based on the compound [XVIII], preferably from 4 to 10 equivalents. The reaction temperature is within a range of from xe2x88x9220xc2x0 C. to 30xc2x0 C., preferably within a range of from xe2x88x925xc2x0 C. to 25xc2x0 C. The reaction time varies depending upon e.g. the reaction temperature and the reaction amount, but may be selected within a range of from 30 minutes to 2 hours in general. After completion of the reaction, the desired product is isolated from the reaction system by a conventional method and may be purified by e.g. column chromatography or recrystallization, as the case requires.
The compound [II] as an intermediate for the compound [I] of the present invention can be produced, for example, in accordance with the following known process, but the process is not limited thereto. 
{wherein each of Lxe2x80x2, G, Q, R1, R2, R3, X and n is as defined above.}
A compound [XII] can be produced by halogenating a compound [XI] (see Jikken kagaku Kouza fourth edition, vol. 19, p. 416-482 (The Chemical Society of Japan) for example) (Step A-1). Further, the intermediate [II] can be produced by reacting the compound [XII] with the compound [IX] in the presence of a base (e.g. an inorganic salt such as sodium carbonate, potassium carbonate or sodium hydrogencarbonate or an alkali metal hydride such as sodium hydride) (Step A-2). Further, an intermediate [II-a] can be produced by reacting the compound [XII] with an alkali metal cyanate salt and the compound [X] in the presence of an inert solvent (see Journal of the Chemical Society of Japan, vol. 87, No. 5, p. 486 (1966) for example) (Step A-3).
The compounds [II] and [IV-a] as intermediates for the compound [I] of the present invention can be produced, for example, in accordance with the following known process, but the process is not limited thereto. 
{wherein each of G, Q, R1, R2, R3, X, Lxe2x80x2 and n is as defined above, and T is a C1-C6 alkyl group.}
A compound [XIV] can be produced by halogenating a compound [XIII] (see Jikken kagaku Kouza, fourth edition, vol. 19, p. 416-482 (The Chemical Society of Japan) for example) (Step B-1). A compound [XV] can be produced by reacting the compound [XIV] with the compound [X] and an alkali metal cyanate salt (see Journal of the Chemical Society of Japan, vol. 87, No. 5, p. 486 (1966) for example) (Step B-2). Otherwise, the compound [XV] can be produced by reacting the compound [XIV] with the compound [IX] in the presence of an inorganic salt such as sodium carbonate, potassium carbonate or sodium hydrogencarbonate or a base such as an alkali metal hydride such as sodium hydride (Step B-3). A compound [XVI] can be produced by reducing the compound [XV] in accordance with a known process (Jikken kagaku Kouza, fourth edition, vol. 26, p. 159-266 (The Chemical Society of Japan) for example) (B-4). A compound [II-b] can be produced by oxidizing the compound [XVI] in accordance with a known process (see Jikken kagaku Kouza, fourth edition, vol. 21, p. 2-23 (The Chemical Society of Japan) for example) (Step B-5). A compound [XVII] can be produced by halogenating the compound [XVI] in accordance with a known process (see Jikken kagaku Kouza, fourth edition, vol. 19, p. 416-482 (The Chemical Society of Japan) for example) (Step B-6).
A compound [IV-a] can be produced by cyanating the compound [XVII] in accordance with a known process (see Jikken kagaku Kouza, fourth edition, vol. 20, p. 437-462 (The Chemical Society of Japan) for example) (Step B-7).
The compound [VII] as an intermediate for the compound [I] of the present invention can be produced, for example, in accordance with the following known process, but the process is not limited thereto. 
(wherein each of R3, Q, X, Y and n is as defined above.)
The compound [VII] of the present invention can be produced by reacting the compound [XI] and the compound [III] (see Jikken kagaku Kouza, fourth edition, vol. 20, p. 349-355 (The Chemical Society of Japan) for example). Here, the material compound [III] to be used in the present production process may form a salt with e.g. hydrochloric acid or sulfuric acid.
The compound [XVIII] as an intermediate for the compound [I] of the present invention can be produced, for example, in accordance with the following known process, but the process is not limited thereto. 
{wherein each of G, R1, R3, Lxe2x80x2, X1, X2, X3 and X4 is as defined above.}
An intermediate [XXI] can be produced by reacting a compound [XX] with an alkali metal cyanate salt and the compound [X] in an inert solvent (see Journal of the Chemical Society of Japan, vol. 87, No. 5, p. 486 (1966) for example) (Step C-1). An intermediate [XXII] can be produced by nitrating the compound [XXI] with e.g. nitric acid, acetyl nitrate or sodium nitrate (see Jikken kagaku Kouza, fourth edition, vol. 20, p. 394-399 (The Chemical Society of Japan) for example) (Step C-2). The intermediate [XVIII] can be produced by reducing the compound [XXII] in accordance with a known process (see Jikken kagaku Kouza, fourth edition, vol. 26, p. 159-266 (The Chemical Society of Japan) for example) (Step C-3).